JPH01285385A - Thermal recording medium - Google Patents
Thermal recording mediumInfo
- Publication number
- JPH01285385A JPH01285385A JP63115723A JP11572388A JPH01285385A JP H01285385 A JPH01285385 A JP H01285385A JP 63115723 A JP63115723 A JP 63115723A JP 11572388 A JP11572388 A JP 11572388A JP H01285385 A JPH01285385 A JP H01285385A
- Authority
- JP
- Japan
- Prior art keywords
- compound
- heat
- dye precursor
- sensitive recording
- recording material
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 150000001875 compounds Chemical class 0.000 claims abstract description 37
- 239000002243 precursor Substances 0.000 claims abstract description 11
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 3
- 239000000126 substance Substances 0.000 claims abstract description 3
- 239000000463 material Substances 0.000 claims description 24
- 125000006575 electron-withdrawing group Chemical group 0.000 claims 1
- 230000004044 response Effects 0.000 abstract description 3
- AGIJRRREJXSQJR-UHFFFAOYSA-N 2h-thiazine Chemical compound N1SC=CC=C1 AGIJRRREJXSQJR-UHFFFAOYSA-N 0.000 abstract description 2
- CZZYITDELCSZES-UHFFFAOYSA-N diphenylmethane Chemical compound C=1C=CC=CC=1CC1=CC=CC=C1 CZZYITDELCSZES-UHFFFAOYSA-N 0.000 abstract description 2
- AAAQKTZKLRYKHR-UHFFFAOYSA-N triphenylmethane Chemical compound C1=CC=CC=C1C(C=1C=CC=CC=1)C1=CC=CC=C1 AAAQKTZKLRYKHR-UHFFFAOYSA-N 0.000 abstract description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 abstract 1
- 229910000040 hydrogen fluoride Inorganic materials 0.000 abstract 1
- -1 ROMO Chemical group 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 8
- 238000003786 synthesis reaction Methods 0.000 description 8
- 230000004043 responsiveness Effects 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 239000004372 Polyvinyl alcohol Substances 0.000 description 6
- 229920002451 polyvinyl alcohol Polymers 0.000 description 6
- 239000000975 dye Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 239000005995 Aluminium silicate Substances 0.000 description 4
- 235000012211 aluminium silicate Nutrition 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical class CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- FWQHNLCNFPYBCA-UHFFFAOYSA-N fluoran Chemical compound C12=CC=CC=C2OC2=CC=CC=C2C11OC(=O)C2=CC=CC=C21 FWQHNLCNFPYBCA-UHFFFAOYSA-N 0.000 description 3
- LYRFLYHAGKPMFH-UHFFFAOYSA-N octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(N)=O LYRFLYHAGKPMFH-UHFFFAOYSA-N 0.000 description 3
- PYSRRFNXTXNWCD-UHFFFAOYSA-N 3-(2-phenylethenyl)furan-2,5-dione Chemical compound O=C1OC(=O)C(C=CC=2C=CC=CC=2)=C1 PYSRRFNXTXNWCD-UHFFFAOYSA-N 0.000 description 2
- CWLKGDAVCFYWJK-UHFFFAOYSA-N 3-aminophenol Chemical compound NC1=CC=CC(O)=C1 CWLKGDAVCFYWJK-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229920000147 Styrene maleic anhydride Polymers 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- ZOJBYZNEUISWFT-UHFFFAOYSA-N allyl isothiocyanate Chemical compound C=CCN=C=S ZOJBYZNEUISWFT-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Natural products OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 239000012188 paraffin wax Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 150000003585 thioureas Chemical class 0.000 description 2
- 239000001993 wax Substances 0.000 description 2
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 2
- LIZLYZVAYZQVPG-UHFFFAOYSA-N (3-bromo-2-fluorophenyl)methanol Chemical compound OCC1=CC=CC(Br)=C1F LIZLYZVAYZQVPG-UHFFFAOYSA-N 0.000 description 1
- CBDLNOVOFXJEOB-UHFFFAOYSA-N 1-methoxy-4-(4-methoxyphenoxy)benzene Chemical compound C1=CC(OC)=CC=C1OC1=CC=C(OC)C=C1 CBDLNOVOFXJEOB-UHFFFAOYSA-N 0.000 description 1
- OAGNKYSIOSDNIG-UHFFFAOYSA-N 1-methyl-3-[2-(3-methylphenoxy)ethoxy]benzene Chemical compound CC1=CC=CC(OCCOC=2C=C(C)C=CC=2)=C1 OAGNKYSIOSDNIG-UHFFFAOYSA-N 0.000 description 1
- RJTICPGQFMYYEG-UHFFFAOYSA-N 1-phenyl-3-prop-2-enylthiourea Chemical compound C=CCNC(=S)NC1=CC=CC=C1 RJTICPGQFMYYEG-UHFFFAOYSA-N 0.000 description 1
- FSLXCIJOWQAYPN-UHFFFAOYSA-N 1-phenyl-4-prop-2-enoxybenzene Chemical group C1=CC(OCC=C)=CC=C1C1=CC=CC=C1 FSLXCIJOWQAYPN-UHFFFAOYSA-N 0.000 description 1
- WCOXQTXVACYMLM-UHFFFAOYSA-N 2,3-bis(12-hydroxyoctadecanoyloxy)propyl 12-hydroxyoctadecanoate Chemical compound CCCCCCC(O)CCCCCCCCCCC(=O)OCC(OC(=O)CCCCCCCCCCC(O)CCCCCC)COC(=O)CCCCCCCCCCC(O)CCCCCC WCOXQTXVACYMLM-UHFFFAOYSA-N 0.000 description 1
- WLTCCDHHWYAMCG-UHFFFAOYSA-N 2-phenylmethoxynaphthalene Chemical compound C=1C=C2C=CC=CC2=CC=1OCC1=CC=CC=C1 WLTCCDHHWYAMCG-UHFFFAOYSA-N 0.000 description 1
- 229940018563 3-aminophenol Drugs 0.000 description 1
- QSNSCYSYFYORTR-UHFFFAOYSA-N 4-chloroaniline Chemical compound NC1=CC=C(Cl)C=C1 QSNSCYSYFYORTR-UHFFFAOYSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 1
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- AZUZXOSWBOBCJY-UHFFFAOYSA-N Polyethylene, oxidized Polymers OC(=O)CCC(=O)C(C)C(O)CCCCC=O AZUZXOSWBOBCJY-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Chemical class 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 125000004453 alkoxycarbonyl group Chemical group 0.000 description 1
- 235000016720 allyl isothiocyanate Nutrition 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 1
- 235000013539 calcium stearate Nutrition 0.000 description 1
- 239000008116 calcium stearate Substances 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 239000005018 casein Substances 0.000 description 1
- BECPQYXYKAMYBN-UHFFFAOYSA-N casein, tech. Chemical compound NCCCCC(C(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(CC(C)C)N=C(O)C(CCC(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(C(C)O)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(COP(O)(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(N)CC1=CC=CC=C1 BECPQYXYKAMYBN-UHFFFAOYSA-N 0.000 description 1
- 235000021240 caseins Nutrition 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 235000019329 dioctyl sodium sulphosuccinate Nutrition 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical class C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- ROORDVPLFPIABK-UHFFFAOYSA-N diphenyl carbonate Chemical compound C=1C=CC=CC=1OC(=O)OC1=CC=CC=C1 ROORDVPLFPIABK-UHFFFAOYSA-N 0.000 description 1
- YHAIUSTWZPMYGG-UHFFFAOYSA-L disodium;2,2-dioctyl-3-sulfobutanedioate Chemical compound [Na+].[Na+].CCCCCCCCC(C([O-])=O)(C(C([O-])=O)S(O)(=O)=O)CCCCCCCC YHAIUSTWZPMYGG-UHFFFAOYSA-L 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000003754 ethoxycarbonyl group Chemical group C(=O)(OCC)* 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000007850 fluorescent dye Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- HSEMFIZWXHQJAE-UHFFFAOYSA-N hexadecanamide Chemical compound CCCCCCCCCCCCCCCC(N)=O HSEMFIZWXHQJAE-UHFFFAOYSA-N 0.000 description 1
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 125000001160 methoxycarbonyl group Chemical group [H]C([H])([H])OC(*)=O 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 235000010981 methylcellulose Nutrition 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- JHOKTNSTUVKGJC-UHFFFAOYSA-N n-(hydroxymethyl)octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCO JHOKTNSTUVKGJC-UHFFFAOYSA-N 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- QHDYIMWKSCJTIM-UHFFFAOYSA-N phenyl 1-hydroxynaphthalene-2-carboxylate Chemical compound C1=CC2=CC=CC=C2C(O)=C1C(=O)OC1=CC=CC=C1 QHDYIMWKSCJTIM-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 229920000570 polyether Chemical class 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 1
- 238000001454 recorded image Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 229940037312 stearamide Drugs 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- KAKZBPTYRLMSJV-UHFFFAOYSA-N vinyl-ethylene Natural products C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 1
- 239000003232 water-soluble binding agent Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
- B41M5/30—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using chemical colour formers
- B41M5/333—Colour developing components therefor, e.g. acidic compounds
- B41M5/3333—Non-macromolecular compounds
- B41M5/3335—Compounds containing phenolic or carboxylic acid groups or metal salts thereof
- B41M5/3336—Sulfur compounds, e.g. sulfones, sulfides, sulfonamides
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Heat Sensitive Colour Forming Recording (AREA)
Abstract
Description
【発明の詳細な説明】
（Ａ）産業上の利用分野
本発明は感熱記録材料に関し、特に熱応答性に優れ良悪
熱記録材料に関する。DETAILED DESCRIPTION OF THE INVENTION (A) Industrial Application Field The present invention relates to a heat-sensitive recording material, and particularly to a heat-sensitive recording material having excellent thermal responsiveness.
（Ｂ）従来技術
感熱記録材料は一般に支持体上に電子供与性の通常無色
ないし淡色の染料前駆体と電子受容性の顕色剤とを主成
分とする感熱記録層を設けたもので、熱ヘツド、熱ペン
、レーザー光等で瞬時反応し、記録画像が得られるもの
で、特公昭４３−４１６０号、特公昭４５−１４０３９
号公報等に開示されている。このような感熱記録材料は
比較的簡単な装置で記録がないことなどの利点があり、
計測用記録計、ファクシミリ、プリンター、コンビ為−
ターの端末機、ラベル、乗車券等自動券売機など広範囲
の分野に利用されている。(B) Conventional technology Heat-sensitive recording materials generally have a heat-sensitive recording layer on a support, the main components of which are an electron-donating, usually colorless or light-colored dye precursor and an electron-accepting color developer. It reacts instantaneously with a head, a hot pen, a laser beam, etc., and a recorded image can be obtained.
It is disclosed in the publication number etc. This type of heat-sensitive recording material has the advantage of being a relatively simple device and requiring no recording.
Measuring recorder, facsimile, printer, combination machine -
It is used in a wide range of fields, including computer terminals, labels, and automatic ticket vending machines for passenger tickets.
感熱記録材料に要求される基本的性能としては、十分な
発色画像濃度及び感度をもつこと、経時による発色画像
の劣化がないことなどがある。また、近年、印字記録の
高速化が進められ記録装置自体の高速化と共にそれに対
応できる記録材料、すなわち低い熱エネルギーで高濃度
の発色画像が得られる熱応答性に優れている感熱記録材
料の開発が望まれている。The basic performances required of a heat-sensitive recording material include sufficient color image density and sensitivity, and no deterioration of color images over time. In addition, in recent years, the speed of print recording has been increasing, and as the speed of recording devices themselves has increased, we have also developed recording materials that can cope with this, that is, heat-sensitive recording materials with excellent thermal responsiveness that can produce high-density colored images with low thermal energy. is desired.
従来より、顕色剤としてはフェノール性化合物、側光ば
、２．２−ビス（４−ヒドロキシフェニル）プロパン等
が用いられてきたが、これらでは熱応容性に優れた感熱
記録材料を得る事は困難であった。Conventionally, phenolic compounds, sidelights, 2,2-bis(4-hydroxyphenyl)propane, etc. have been used as color developers, but with these, heat-sensitive recording materials with excellent heat response can be obtained. Things were difficult.
また、近年、チオ尿素誘導体を顕色剤として用いる試み
が提案されている。（特開昭５９−１３３０９６、特開
昭５９−１９０８９３、特開昭６Ｏ−１４５８８４）
しかし、これらによってもなお、熱応答性に優れた感熱
記録材料を得る事は困難であった。Furthermore, in recent years, attempts have been made to use thiourea derivatives as color developers. (JP-A-59-133096, JP-A-59-190893, JP-A-6O-145884) However, even with these methods, it was still difficult to obtain a heat-sensitive recording material with excellent thermal responsiveness.
しかし、チオ尿素誘導体のうち、Ｎ−アリル−Ｎ′−フ
ェニルチオ尿素訪導体については添加剤としての応用が
特開昭５７−１０５３９１において提案されているのみ
であった。ここで提案されている化合物はフェニル基上
に置換基を持たないか、又は置換基として、水酸基以外
の電子供与性基を持つものであった。この特許公報にお
いて提案さ的でなかった。However, among the thiourea derivatives, the application of N-allyl-N'-phenylthiourea visiting conductor as an additive was only proposed in JP-A-57-105391. The compounds proposed here either have no substituent on the phenyl group or have an electron-donating group other than a hydroxyl group as a substituent. The proposal in this patent publication was not targeted.
（Ｃ）発明の目的
本発明の目的は、熱応答性に優れた感熱記録材料を得る
事にある。(C) Purpose of the Invention The purpose of the present invention is to obtain a heat-sensitive recording material having excellent thermal responsiveness.
（Ｄ）発明の構成
通常無色ないし淡色の染料前駆体と加熱時反応して該染
料前駆体を発色せしめる顕色剤を含有する感熱記録材料
において、該顕色剤として下記−般式で表わされる化合
物を含有させる事により、熱応答性に優れた感熱記録材
料を得ることができた。(D) Structure of the Invention In a heat-sensitive recording material containing a color developer that reacts with a normally colorless or light-colored dye precursor upon heating to cause the dye precursor to develop color, the color developer is represented by the following general formula: By incorporating the compound, a heat-sensitive recording material with excellent heat responsiveness could be obtained.
ロモなどのハロゲン原子、メトキシカルボニル、エトキ
シカルボニルなどのアルコキシカルボニル酸基などがあ
る。Examples include halogen atoms such as ROMO, and alkoxycarbonyl acid groups such as methoxycarbonyl and ethoxycarbonyl.
上記一般式で表わされる化合物の具体例を以下に例示す
る。Specific examples of the compound represented by the above general formula are illustrated below.
化合物（１）
化合物（２）
化合物（３）
化合物（４）
化合物（５）
化合物（６）
化合物（７）
化合物（８）
化合物（９）
化合物（１０）
化合物（１１）
化合物（１２）
化合物（１３）
化合物（１４）
本発明による化合物は公知の方法により容易に合成出来
る。Compound (1) Compound (2) Compound (3) Compound (4) Compound (5) Compound (6) Compound (7) Compound (8) Compound (9) Compound (10) Compound (11) Compound (12) Compound ( 13) Compound (14) The compound according to the present invention can be easily synthesized by a known method.
本発明による化合物は、通常染料前駆体に対してｓｉｆ
！ｋｓ以上含有される。好ましい量は、１０〜６００重
ｆ％であり、特に２０〜５００重量係が好ましい。The compounds according to the invention usually have sif for dye precursors.
! Contains more than ks. A preferable amount is 10 to 600% by weight, particularly preferably 20 to 500% by weight.
含有量が５重量％未満では、熱応答性、画像保存性が十
分でなく、６００重ｆｆ％より多い含有量では熱ヘツド
等への熱可融物付着が増加し、印字障害が生じる場合も
ある。If the content is less than 5% by weight, thermal responsiveness and image storage stability will be insufficient, and if the content is more than 600% by weight, the adhesion of thermofusible substances to thermal heads, etc. will increase, and printing problems may occur. be.
本発明の感熱記録材料に用いられる主な成分を以下に具
体的に説明するが、これらに限定されるものではない。The main components used in the heat-sensitive recording material of the present invention will be specifically explained below, but are not limited thereto.
染料前駆体としては、トリフェニルメタン系、フルオラ
ン系、ジフェニルメタン系、チアジン系、スピロピラン
系化合物などが挙げられる。例えば、クリスタルバイオ
レットラクトン、３−ジエチルアミノ−７−メチルフル
オラン、３−ジエチルアミノ−６−クロロ−７−メチル
フルオラン、３−ジエチルアミノ−６−メチル−７−ク
ロロフルオラン、３−ジエチルアミノ−７−アニリノフ
ルオラン、３−ジエチルアミノ−７−（２−クロロアニ
リノ）フルオラン、３−ジブチルアミノ−７−（２−ク
ロロアニリノ）フルオラン、３−ジエチルアミノ−７−
（３−クロロアニリノ）フルオラン、３−ジエチルアミ
ノ−６−メチル−７−アニリノフルオラン、３−（Ｎ−
エチル−ｐ−）ルイジノ）−６−メチル−７−アニリノ
フルオラン、３−（Ｎ−メチルシクロヘキシルアミノ）
ｉ−メチル−７−アニリノフルオラン、３−ピペリジノ
−３−メチル−７−アニリノフルオラン、３−ジブチル
アミノ−６−メチル−７−アニリノフルオラン、３−（
Ｎ−メチル−Ｎ−プロピル）アミノ−６−メチル−７−
アニリノフルオラン、３−（Ｎ−エチル−Ｎ−イソプロ
ピル）アミノ−６−メチル−７−アニリノフルオラン、
３−（Ｎ−エチル−Ｎ−テトラヒドロフルフリル）アミ
ノ−６−メチル−７−アニリノフルオラン等がある。Examples of the dye precursor include triphenylmethane-based, fluoran-based, diphenylmethane-based, thiazine-based, and spiropyran-based compounds. For example, crystal violet lactone, 3-diethylamino-7-methylfluorane, 3-diethylamino-6-chloro-7-methylfluorane, 3-diethylamino-6-methyl-7-chlorofluorane, 3-diethylamino-7- Anilinofluoran, 3-diethylamino-7-(2-chloroanilino)fluoran, 3-dibutylamino-7-(2-chloroanilino)fluoran, 3-diethylamino-7-
(3-chloroanilino)fluoran, 3-diethylamino-6-methyl-7-anilinofluoran, 3-(N-
Ethyl-p-)luidino)-6-methyl-7-anilinofluorane, 3-(N-methylcyclohexylamino)
i-Methyl-7-anilinofluorane, 3-piperidino-3-methyl-7-anilinofluorane, 3-dibutylamino-6-methyl-7-anilinofluorane, 3-(
N-methyl-N-propyl)amino-6-methyl-7-
Anilinofluorane, 3-(N-ethyl-N-isopropyl)amino-6-methyl-7-anilinofluorane,
Examples include 3-(N-ethyl-N-tetrahydrofurfuryl)amino-6-methyl-7-anilinofluorane.
バインダーとしては、デンプン類、ヒドロキシエチルセ
ルロース、メチルセルロース、カルボキシメチルセルロ
ース、ゼラチン、カゼイン、ポリビニルアルコール、変
性ポリビニルアルコール、スチレン無水マレイン酸共重
合体、エチレン−無水マレイン酸共重合体などの水溶性
バインダー、スチレン−ブタジェン共重合体、アクリロ
ニトリル−ブタジェン共重合体、アクリル酸メチル−ブ
タジェン共重合体などのラテックス系水不溶性バインダ
ーなどが挙げられる。Examples of binders include starches, hydroxyethyl cellulose, methyl cellulose, carboxymethyl cellulose, gelatin, casein, polyvinyl alcohol, modified polyvinyl alcohol, water-soluble binders such as styrene-maleic anhydride copolymer, ethylene-maleic anhydride copolymer, and styrene-maleic anhydride copolymer. Latex-based water-insoluble binders such as butadiene copolymer, acrylonitrile-butadiene copolymer, methyl acrylate-butadiene copolymer, and the like can be mentioned.
顔料としては、ケイソウ土、メルク、カオリン、焼成カ
オリン、炭酸カルシウム、炭酸マグネシウム、酸化チタ
ン、酸化亜鉛、酸化ケイ素、水酸化アルミニウム、尿素
−ホルマリン樹脂などが挙げられる。Examples of the pigment include diatomaceous earth, Merck, kaolin, calcined kaolin, calcium carbonate, magnesium carbonate, titanium oxide, zinc oxide, silicon oxide, aluminum hydroxide, urea-formalin resin, and the like.
ま九、感度を更に向上させる為に、添加剤としてＮ−ヒ
ドロキシメチルステアリン酸アミド、ステアリン酸アミ
ド、パルミチン酸アミド等のワックス類、２−ベンジル
オキシナフタレン、１−ヒドロキシ−２−フェノキシカ
ルボニルナフタレン等のす７ト一ル誘導体、ｐ−ベンジ
ルフェニル、４−アリルオキシビフェニル等のビフェニ
ル誘導体、１．２−ビス（３−メチルフェノキシ）エタ
ン、２．２′−ビス（４−メトキシフェノキシ）ジエチ
ルエーテル、ビス（４−メトキシフェニル）エーテル等
のポリエーテル化合物、炭酸ジフェニル、シエウｒＲジ
Ｃｐ−クロルベンジル）エステル等の炭酸又は、シ晶つ
酸ジエステル誘導体等を添加する事ができる。9. In order to further improve sensitivity, waxes such as N-hydroxymethylstearamide, stearamide, palmitic acid amide, 2-benzyloxynaphthalene, 1-hydroxy-2-phenoxycarbonylnaphthalene, etc. are used as additives. Nosu 7 tol derivatives, p-benzylphenyl, biphenyl derivatives such as 4-allyloxybiphenyl, 1,2-bis(3-methylphenoxy)ethane, 2,2'-bis(4-methoxyphenoxy) diethyl ether , polyether compounds such as bis(4-methoxyphenyl) ether, carbonic acid or citric acid diester derivatives such as diphenyl carbonate, and seu rR diCp-chlorobenzyl) ester.
その他に、ヘッド摩耗防止、スティッキング防止などの
目的でステアリン酸亜鉛、ステアリン酸カルシウム等の
高級脂肪酸金属塩、パラフィン、酸化パラフィン、ポリ
エチレン、酸化ポリエチレン、ステアリン酸アミド、カ
スターワックス等のワックス類を、また、ジオクチルス
ルホコハク酸ナトリウム等の分散剤、ベンゾフェノン系
、ベンゾトリアゾール系などの紫外線吸収剤、さらに界
面活性剤、蛍光染料などが挙げられる。In addition, higher fatty acid metal salts such as zinc stearate and calcium stearate, waxes such as paraffin, oxidized paraffin, polyethylene, oxidized polyethylene, stearic acid amide, and castor wax are used to prevent head wear and stickiness. Examples include dispersants such as sodium dioctyl sulfosuccinate, ultraviolet absorbers such as benzophenone and benzotriazole, surfactants, and fluorescent dyes.
本発明による感熱記録材料に用いられる支持体としては
、紙が主として用いられるが、各種不織布、プラスチッ
クフィルム、合成紙、金属箔等あるいはこれを組合わせ
た複合シートを任意に用いることができる。Paper is mainly used as the support for the heat-sensitive recording material according to the present invention, but various nonwoven fabrics, plastic films, synthetic papers, metal foils, etc., or composite sheets made of combinations thereof can also be used as desired.
なお、紙又は合成紙などの上に焼成カオリンなどを塗布
したものを支持体としてもよい。Note that the support may be paper or synthetic paper coated with calcined kaolin or the like.
（Ｅ）合成例及び実施例
合成例及び実施例によって本発明を更に詳しく説明する
。(E) Synthesis Examples and Examples The present invention will be explained in more detail with reference to Synthesis Examples and Examples.
合成例１ 化合物（１）の合成
ｐ−クロロアニリン２０．４ ｆとアリルイノチオシア
ネ−）１５．８４Ｆとをエタノール１６０ゴに加え、８
分間加熱攪拌し還流条件下においた。水を加え放冷し析
出した目的物の結晶を戸数して得た。Synthesis Example 1 Synthesis of Compound (1) 20.4 F of p-chloroaniline and 15.84 F of allylinothiocyanate were added to 160 g of ethanol, and 8
The mixture was heated and stirred for a minute under reflux conditions. Water was added and the mixture was allowed to cool to obtain crystals of the desired product.
これを更にエタノールと水の混合溶媒で再結晶し目的物
２２．５９を得た。ｍ、ｐ、＝１００．５〜１０２．０
℃合成例２ 化合物（２）の合成
合成例１で用いたｐ−クロロアニリン２０．４９のかわ
りにｐ−アミノ安息香酸エチル２６．４ｆを用いた以外
は合成例１と同様にして化合物（２１８，６２を得た６
ｍ、ｐ、＝９１．５〜９３．０℃合成例３ 化合物（
３）の合成
ｍ−アミノフェノール１３．０８ ｔとアリルイソチオ
シアネート１１．８８ ｔとをエタノール１００ゴに加
え、１０分間加熱攪拌し、還流条件下においた。その後
、溶媒を留去し、残渣をベンゼンで処理して目的物を得
た。これをベンゼンとエタノールの混合溶媒で再結晶し
目的物１３．５ ｆを得た。This was further recrystallized from a mixed solvent of ethanol and water to obtain the desired product 22.59. m, p, = 100.5 to 102.0
°C Synthesis Example 2 Synthesis of Compound (2) Compound (218 ,6 got 62
m, p, = 91.5-93.0°C Synthesis Example 3 Compound (
Synthesis of 3) 13.08 t of m-aminophenol and 11.88 t of allyl isothiocyanate were added to 100 g of ethanol, heated and stirred for 10 minutes, and placed under reflux conditions. Thereafter, the solvent was distilled off, and the residue was treated with benzene to obtain the desired product. This was recrystallized with a mixed solvent of benzene and ethanol to obtain the desired product 13.5f.
ｍ、ｐ、＝ １０３．０〜１０３．５℃実施例１
３−ジブチルアミノ−６−メチル−７−アニリノフルオ
ラン３０Ｆを、１．５２のポリビニルアルコールを含む
水７０ｔと共にペイントコンディジ冒ナーで分散した。m, p, = 103.0 to 103.5°C Example 1 3-dibutylamino-6-methyl-7-anilinofluorane 30F was mixed with 70 tons of water containing 1.52% polyvinyl alcohol in a paint conditioner. It was dispersed.
一方、化合物（１）４０ｆを２ｔのポリビニルアルコー
ルを含む水６０ｆと共に、ペイントコンディジ曹ナーで
分散した。On the other hand, 40f of compound (1) was dispersed with 60f of water containing 2t of polyvinyl alcohol using a paint conditioner.
これら２種の分散液を混合した後、炭酸カルシウムの４
０％分散液７５１を加え、更にステアリン酸亜鉛の４０
％分散液２５ｆ、１０％ポリビニルアルコール水溶液１
１０Ｆ及び水３００２を加え、十分攪拌して塗液とした
。After mixing these two types of dispersions, 4
0% dispersion 751 was added, and then 40% of zinc stearate was added.
% dispersion 25f, 10% polyvinyl alcohol aqueous solution 1
10F and water 3002 were added and sufficiently stirred to prepare a coating liquid.
一方、坪量４２々冒の紙に焼成カオリン１００ｆとポリ
ビニルアルコール１０チ水溶液２００ｆの混合物を攪拌
の後、乾燥後の塗布量が５に背となる様に塗布乾燥し、
支持体とした。On the other hand, after stirring a mixture of 100 f of calcined kaolin and 200 f of an aqueous solution of polyvinyl alcohol 10 g on paper with a basis weight of 42 mm, the mixture was applied and dried so that the coating amount after drying was 5 mm.
It was used as a support.
得られた支持体に、先に得た塗液な塗布乾燥した。（固
形分塗布量が２．２に背となる様に調整した。）これを
スーパーカレンダーで処理して感熱記録材料を得た。The previously obtained coating solution was applied to the obtained support and dried. (The solid content coating amount was adjusted to 2.2.) This was treated with a super calendar to obtain a heat-sensitive recording material.
実施例２
実施例１で用いた化合物（１）４０ｆのかわりに化合物
（２）４０ｆを用いた以外は実施例１と同様にして感熱
記録材料を得た。Example 2 A heat-sensitive recording material was obtained in the same manner as in Example 1 except that 40f of compound (2) was used in place of 40f of compound (1) used in example 1.
実施例３
実施例りで用いた化合物（１）４（ｌのかわりに化合物
（３１４０Ｆを用いた以外は実施例１と同様にして感熱
記録材料を得た。Example 3 A heat-sensitive recording material was obtained in the same manner as in Example 1 except that Compound (3140F) was used in place of Compound (1) 4(l) used in Example.
比較例１
実施例１で用いた化合物（１）４０９のかわりにＮ−ア
リル−Ｎ’−（ｐ−エトキシフェニル）チオ尿素４０Ｆ
を用いた以外は実施例１と同様にして感熱記録材料を得
た。Comparative Example 1 N-allyl-N'-(p-ethoxyphenyl)thiourea 40F instead of compound (1) 409 used in Example 1
A heat-sensitive recording material was obtained in the same manner as in Example 1 except that .
比較例２
実施例１で用いた化合物（１）４０２のかわりにＮ−ア
リルーＮ／−（ｐ−メチルフェニル）チオ尿素４０１を
用いた以外は実施例１と同様にして感熱記録材料を得た
。Comparative Example 2 A heat-sensitive recording material was obtained in the same manner as in Example 1 except that N-allyl N/-(p-methylphenyl)thiourea 401 was used in place of Compound (1) 402 used in Example 1. .
比較例３
実施例１で用いた化合物（１） ４ Ｏｆのかわりに２
゜２−ビス（４−ヒドロキシフェニル）フロパン４０ｆ
を用いた以外は実施例１と同様にして感熱記録材料を得
た。Comparative Example 3 Compound (1) used in Example 1 2 instead of 4 Of
゜2-bis(4-hydroxyphenyl)furopane 40f
A heat-sensitive recording material was obtained in the same manner as in Example 1 except that .
（評価）
実施例１〜３及び比較例１〜３で作成した感熱記録材料
を０３ＦＡＸ試験機で画像濃度を比較した。試験機は大
金ｔＬ機製（ＴＨ−ＰＭＤ）で、ドツト＠度が８ドツ）
／ａｉ、ヘッド抵抗は１８５Ωのサーマルヘッドを使
用し、ヘッド電圧１１ｖ、通電時間１．０ｍ、−ｓ、で
印字した。(Evaluation) The image densities of the heat-sensitive recording materials prepared in Examples 1 to 3 and Comparative Examples 1 to 3 were compared using a 03 FAX tester. The test machine was made by Daikin tL Machine (TH-PMD), and the temperature was 8 dots)
/ai, a thermal head with a head resistance of 185Ω was used, and printing was performed at a head voltage of 11 V and a current application time of 1.0 m, -s.
なお、画像濃度については、マクベスＲＤ−５１４屋反
射濃度計を用いて測定した。The image density was measured using a Macbeth RD-514 reflection densitometer.
（Ｆ）発明の効果
表で示される様に本発明による化合物を用いる事により
熱応答性に優れた感熱記録材料が得られる。(F) As shown in the Table of Effects of the Invention, by using the compound according to the present invention, a heat-sensitive recording material with excellent heat responsiveness can be obtained.
Claims (1)
染料前駆体を発色せしめる顕色剤とを含有する感熱記録
材料において、該顕色剤として、下記一般式で表わされ
る化合物を含有する事を特徴とする感熱記録材料。 一般式 ▲数式、化学式、表等があります▼ （但し、Ｒは電子吸引性基又は水酸基を表わす。）[Scope of Claims] A heat-sensitive recording material containing a normally colorless or light-colored dye precursor and a color developer that reacts with the dye precursor to develop color when heated, wherein the color developer is expressed by the following general formula: A heat-sensitive recording material characterized by containing the represented compound. General formula▲There are mathematical formulas, chemical formulas, tables, etc.▼ (However, R represents an electron-withdrawing group or a hydroxyl group.)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63115723A JPH01285385A (en) | 1988-05-11 | 1988-05-11 | Thermal recording medium |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63115723A JPH01285385A (en) | 1988-05-11 | 1988-05-11 | Thermal recording medium |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH01285385A true JPH01285385A (en) | 1989-11-16 |
Family
ID=14669530
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63115723A Pending JPH01285385A (en) | 1988-05-11 | 1988-05-11 | Thermal recording medium |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01285385A (en) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59169890A (en) * | 1983-03-16 | 1984-09-25 | Ricoh Co Ltd | Thermal recording material |
-
1988
- 1988-05-11 JP JP63115723A patent/JPH01285385A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59169890A (en) * | 1983-03-16 | 1984-09-25 | Ricoh Co Ltd | Thermal recording material |
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